-4-amine salts of the 4-cyclohexyl-cyclohexane carbamic acids



2,838,562 Patented June 10, 1958 (BICYCLOHEXYMA-AMENE SALTS OF THE 4- CYCLOHEXYL-CYCLUEEEXANE CARBAMIC hydrogen chloride salts, and the salts thereafter converted to the free amine. The hydrogen chloride salts of the alpha and beta isomers of the amine melt at 295 -300 C. and 228 232 C., respectively, While the alpha isomer of ACIDS 5 the amine melts at 5 862 C. and the beta isomer of the amine melts at 32 C. Harry F. Brust, Midland, Mich, assignor to The The following examples illustrate the invention but are glifmical Company, Midland, Mich, a corporation of t to b construed as limiting;

e aware Example 1.(Bicyclohexyl)-4-amiize salt of 4-cyclohexyl- N0 Drawiilg- Application 'y 1957 10 cyclohexanecarbamic acid tit-isomer Serial No. 638,672

1.5 moles of gaseous carbon dioxide was slowly bubbled 2 Ciaims- 254F601) into a solution containing 10 grams (0.0553 mole) of (bicyclohexyl)-4-amine ix-isomer in 100 milliliters of diethyl The present invention is directed to the (bicyclohexyl)- ether. The addition was carried out with stirring and 4-amine salts of the 4-cyclohexylcyclohexane carbarnic cooling and at a temperature of 0 C. During the addiacids having the formula tion, a (bicyclohexyl)-4-amine salt of 4-cycl-ohexylcyclo- H2 H2 H H H H H H H (I) A 2 I 2 I 2 I 2 I 2 432 i \H CC\ H CC\H\ /0 O\ /O-C C-NCOH-HzN-C (3-0 G (ll-(I3 \H\CC/ H CO/ \H\C-C/ \H2 H2 2 2 III: EIH Iiiz I a These new compounds are somewhat soluble in many hexanecarbamic acid a-isomer product precipitated in the organic solvents and of very low solubility in water. reaction mixture as a white crystalline solid. Toward the They have been found to be active as parasiticides and end of the addition, no further substantial amounts of are adapted to be employed as active toxic constituents of product precipitated in the reaction mixture. The product compositions for the control of many pests such as Alterwas thereafter separated by filtration, dried and found to naria solani. melt at 104 C. with some slight decomposition.

The new compounds may be prepared by reacting carbon dioxide with bicyclohexyl-4-amine. The reaction is Example 2(Bwycl0hexyl)'4'.amm.e Salt. of 4'cyclohex' carried out in the presence of an organic solvent inert ylcyclohexanecarbamw acld fi'lsomer under the conditions of reaction such as toluene, benzene, 15 moles of carbon dioxide is Slowly bubbled into a dioxane or diethyl ether. The reaction is somewhat exosolution of 10 grams 055 mole) f (bicyclohexyl)- thermlc and takes Place smoothly at the temperature 4-amine ,B-isomer in 100 milliliters of diethyl ether. The range of from The tempera? may be addition is carried out with stirring and cooling and at controlled by regulation of the rate of contacting the rea temperature f 0 C, D i the addition, a (bicycloactants and by external cooling. Good results are ob- 40 heyxl) 4 amine salt f 4 cyclohexylcyclohexanecarbamic i h at least molecular PropOrtlon ofFarbgn acid p-isomer precipitates as a white crystalline solid. 1S employfid Wlth two molecular Propomons of Toward the end of the addition, no further substantial 'bicyclohexyl-4 amme. amounts of product precipitates in the reaction mixture. E Y the reaciloni the (blcyclohexyn'4' The product is thereafter separated by filtration and amine is dissolved in the reactlon solvent and gaseous cardried (Bicyclohexyl) 4 amine Salt f 4- 1 1 1 hon dioxide slowly passed" into the solvent solution at a hexanecarbamic acid 545cm has a molecular weight temperature from -l0 to 75 C. During the addition, of 406. the desired product precipitates in the reaction mixture as The new (bicyC1Oh@Xy1) 4 amine Salts f 4 cyclohexyl a Crystalline Solidp completion of the reaction as is cyclohexanecarbamic acid are effective as parasiticides evidenced by the cessation of the precipitation of further f the control f many common pesm For such use P the Product may F recovered by confemional the products may be dispersed on an inert finely divided methods and thereafter purified by recrystallization from Solid and employed as dusts Also, Such mixtures may Suitable Qrgamc Solventsbe dispersed in water with the aid of a wetting agent, The 1 y xy employed as astartmg and the resulting aqueous suspensions employed as terial in the present invention occurs in two isomeric Sprays In other procedures, the Products may b forms known as the alpha and beta lsomers- These two ployed as constituents of oil-in-water emulsions or water lsomel's may be P p by known P In Such dispersions with or Without the addition of wetting, dismethods, 4-cyclohexylcyclohexanol 1S (la/hydrogenated persing or emulsifying agents. In representative operaover a PP Catalyst t to form 4-cyclohexyltions, 100 percent controls of tomato early blight (AlcYcl'ohexallone, and 11113 Product thefeaflfil mm ternaria salami) have been obtained with aqueous spray mated P a 4-CYC1Oh'BXY1CYC1OhEXaIlOflc lmmecompositions containing 0.5 pound of the (bicyclohexyl)- The latter 1S thereafter hydrogenated Over Hickfil 4-amine salt of 4-cyclohexylcyclohexanecarbamic acid catalyst at and 75 Pounds Pressure P Square u-isomer per 100 gallons of ultimate mixture. inch to give a reaction mixture containing about 1 l i l amounts of alpha and beta isomers 1. A (bicyclohexyl)-4-amine salt of 4cyclohexylcyclocyclohexyl)-4-amine. The hydrogen chloride salt of hexanecarbamic id the beta isomer of the. amine is soluble in chloroform 2, (Bicyclohexyl)-4-amine salt of 4-Cyclohexylcycl while the hydrogen chloride salt of the alpha isomer of hexanecarbamic id 4 7 the amine is substantially insoluble in chloroform. Thus,

No references cited.

the isomeric amines may be separated in the form of their 

1. A (BICYCLOHEXYL)-4-AMINE SALT OF 4-CYCLOHEXYLCYCLOHEXANECARBAMIC ACID. 